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Патент USA US3083649

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iJnited States hatent
3,083,639
Patented Apr. 2, i963
1
2
3,983,639
tion may have their surfaces severely abraded and yet will
produce legible copy against a clean background thus
demonstrating that the treatment has penetrated and the
PRGQESS F?i‘t MAE‘HNG FLANOGRAPHEC
PRENTING PLATES
planograp'hic properties have been imparted in depth.
John Frank Thuriow, Gorharn, Maine, assignor to Fitch
hurg Paper Company, Fitchhurg, Mass, a corporation
It is ‘a primary objective of the present invention to im
prove planographic printing plates and, more particularly,
of Massachusetts
to devise manufacturing methods which eliminate many
No Drawing. Filed .luly 6, 1959, Ser. No. 824,942
1% Claims. (Cl. 191-149.?!)
of the operations which are often necessary in conven
tional processes as practiced up to the present time in the
This invention relates to planographic printing plates 10 manufacture of commercially-available printing plates.
and to greatly simpli?ed processes for their manufacture.
This invention is particularly concerned with novel meth
ods for the development of planographic properties in and
on the coatings of coated papers; said coated papers and
their surfaces, prior to treatment 2by certain novel proc 15
esses, being essentially non~planographic in character and
therefore not usable, in a practical sense, as planographic
printing plates. Most particularly my invention relates to
the manufacture of coated paper planographic printing
When paper or other flexible support is coated with
planographic or other coatings in order to obtain a piano
graphic surface suitable for conventional offset printing
such coatings are nearly always applied from aqueous me
dium. As a con-sequence of the use of aqueous coatings
it is often necessary to calender or to perform other oper
ations on paper thus coated in order to obtain ?atness,
reduce curl and so on; furthermore it is often necessary
to apply several coats to the side which bears the plano
plates by treating, after it has been coated and dried, an 20 graphic surface in order to obtain the desired character
essentially non-planographic coated sheet with an essen
istics. With the various operations of coating the back
tially non-aqueous solution containing silicate esters and
side, coating the front side one or more times, sometimes
their reaction products.
By specifying coated paper having a “non-planographic”
coating 1 mean a coating which, when applied to la sup
calender-ing ‘between coating operations, rewinding after
each operation, etc., the manufacturing operation may
25 comprise between ?ve and ?fteen separate steps. Through
port-‘base and dried in conventional equipment, ‘does not
the practice of the art as hereinafter taught it is possible
exhibit the characteristics common to coated planographic
to make excellent planographic plates on ‘a paper or other
?exible base and to do so without the many separate steps
printing plates; the salient above-mentioned “characteris
tics” are the ability to retain a greasy image, whether ‘ap
of manufacture previously necessary. Furthermore, plates
plied by lithographic pen, pencil or typewriter, and to 30 made ‘by my methods have desirable properties not pre
retain non-image areas in a clean hydrophilic condition
viously obtainable ‘by the more involved manufacturing
when run on a conventional offset press. By contrast to
planographic coated printing plates, non-planographic
processes.
The attainment of my objectives and subsequent advan
coated papers soon develop a black tone or scum if at
tages thereof ‘will be readily understood from the follow
tempts are made to use them as plates on conventional 35 ing descriptions and examples and the novel features will
offset presses; in other cases non-planographic coated
papers may not retain the image hereinbefore ‘described.
be more particularly pointed out in the appended claims.
In accordance with my invention it is essential to pro
My invention consists, in part, of methods of imparting
vide a ?exible base or support means which, in addition to
planographic properties to non-planographic coatings.
being water-resistant and strong, is capable of retaining
By specifying an “essentially non-aqueous” solution or 40 in a suitably bonded condition a non-planognaphic coat
solutions I mean solutions of organic solvent or solvents
ing, examples of which are hereinafter provided. In gen
having less than 50% by volume of water but preferably
eral terms, I prefer a paper support ‘base; said paper
having less than 10% of water. One of the objectives of
should ‘be well-sized to assure water resistance and may
my invention is to take advantage of the superior pene
or may not have so-called wet strength. Any ?at, dimen
trating powers of solutions of organic solvents containing 45 sionally stable, good quality, strong, Well-sized sheet will
no water or only a minor amount thereof in the order of
do. I prefer that the paper weigh between 25 and 80
5-25% by volume; such solutions, in contrast with aque
pounds per 3300 square feet. It will, of course, vbe obvious
ous solutions, penetrate thoroughly and with striking ra
that non-planographic coatings such as I shall specify can
pidity dried coatings of the type I shall specify.
be applied to other supports such as fabric or lightweight
50
The use of silicates or silica in planographic printing
metal.
plate art is by no means novel although there are no pre
For the non-planographic coating I prefer one contain
vious records which teach the use of organic esters of
ing as its primary ingredients one or more mineral pig
silica. Thus U.S. Patent No. 2,681,617 teaches the use of
ments and between 12 and 35 parts of one or more ad
a silica aquasol, applied to a planographic surface to form
55 hesives per 100 parts of dry pigment. I apply this coat
a discontinuous deposit while US. Patent No. 2,132,443
ing to at least one, but preferably to both sides of the
discloses that silica, freshly precipitated in a thin ?lm or
paper or other base by any of the conventional methods
coating, under certain conditions forms a lithographic
such that bet-ween 8 and 24 pounds per 3300 square feet
surface. In the present invention the silica or silicate
of each surface remains after drying; thus if 12 pounds
compounds which remain in and on the planographic sur
per 3300 square feet of each surface is applied to a. 60'
face behave quite differently and produce results quite dif
pound sheet the resulting weight per 3300 square feet
‘would be 84 pounds.
ferent from those disclosed in the before-mentioned pat
For the mineral pigment of the above-mentioned non
ents. In the present invention the application is made
planographic coating I prefer clays of the type commonly
only to non-planographic coatings supported on a flexible
base; the treatment is not merely that of a surface cover 65 used in the coating and filling of papers. Other pigments
ing but thoroughly penetrates the coating and often its
or mixtures of pigments which I have used with more or
base support and thus closely resembles ‘a saturation rather
less
dioxide,
success
diatomaceous
include zinceart
oxide,
, kaolin,
barium
calcium
sulfate,carbonate,
silica, silica gel, magnesium carbonate and calcium sul
than a surface treatment. The saturation feature is a vital
part of the present invention for the reason that a mere
fate. But for reasons of economy and performance I pre
surface covering, deposit, or ?lm would be removed by 70 fer clays as the chief pigment.
erasure or by the abrasion of normal press operations
whereas planographic plates made by the present inven
For the adhesive I prefer a protein such as casein or
soy-bean protein. When, however, protein is the sole
3,083,639
3
4
adhesive, plates having inferior performance may result,
which, is to, say that the image may not be adequately
However, for reasons of economy and simplicity I prefer
to use, whenever possible, only such commonly-used sol
vents as methyl and ethyl- alcohol, acetone and dimethyl
{e‘tgineplor the coating may crack when folded; in conse
quence, I generally prefer .to use, along with the pro
ketone; generally a mixture of an alcohol and a ketone
plus the active ingredients ofrthe solution are all that is
tein, a more ?exible adhesive such as a synthetic latex
containing polyvinyl chloride or polyvinyl acetate or a
polyester resin, or a styreneabutadiene copolymer, .or an
required for excellent results.
'
The active ingredients of my planographic solution are
alkydrresin or other high polymers which impart su?icient
silicate esters and/ or their hydrolysis products and may
strength and ‘?exibility. Other ingredients may be added
include the compounds resulting from the’ reaction of
to impart; plasticity, reduce foaming or viscosity of the 10 these silicate esters and their hydrolysis products with
wet coating mixture or to impart other desirable proper
hydroxides of ammonia, barium, sodium or other alka
ties so long as there is no interference with planog'raphic
line materials. Among other things these silicate esters
properties when plates are, eventually, made.
are characterized by their solubility in organic solvents
,It will be obvious to those skilled in the. art that. my . and their insolubility or slight solubility in water. Ex
processcan be extended to numerous non-planographic 15 amples of these esters are tetraethyl orthosilicate; con
coatings wherein the adhesive, such as starch and starch
densed ethyl silicate and ethyl silicate 40 as manufac—
‘derivatives, is other than those speci?cally listed above.
turedand sold by Carbide & Carbon Chemicals Co.'of
As speci?c examples of: the non-planographic coatings
New York ‘City. These silicate esters are liquids having
which I have applied to a ?exible base and, later, have
solvent and penetrating properties and, for the most part,
treated to impart vplanographic properties with more or 20 distill below 200° C. at'760 mm. pressure; calculated as
less success I give the following:
SiO2 their silica contents range between 25 and 55%
by weight with the content generally falling between
[Parts by weight (dry)]
Clay
28.0 and 40.0% .
'
V
_
It will be clear to those skilled in the art that silicate
Synthetic 25 esters other than those speci?cally listed may be used in
practicing the art to be here taught but, without being
limited thereto, ‘I prefer generally to use condensed ethylv
silicate for the preparation of my planographic solutions.
Latex
' In preparing my planographic solutions and in their
30
ultimate application to the non-planographic coated
paper I can follow any one ,of several procedures and still
obtain substantially the same end-result as will now be
shown. In one case, for example, it is possible to react
partially the ethyl silicate with water, apply it- to the
coated ‘base, remove the excess and then to complete the
essential chemical reactions by applying, before drying
In preparation oflcoatings 1 through 10 I have achieved
can’ occur, a second solution containing alkaline agents
excellent-success by using, as the synthetic latex, materials
such as ammonium or barium hydroxide; following this
such as styrene-butadiene copolymers of'which the prod 4-0 second bath’ the excess solution is again removed and
not known as 512-‘R manufactured'by the Dow Chemical
the paper thus treated is dried; on cutting into suitable
Co. of Midland, Michigan, is an example. As previously
indicated, other materials having suitable ?exibility and
compatibility willwork as Well.
sizes, paper thus treated may vbe used on a conventional
Offset pressas a printing plate. Alternatively I may sub
The ‘coatings indicated in Examples 1 through 10. 45 stitute an ammonia vapor or other alkaline vapor treat
ment ‘for the second bath; this procedure avoids the prob
were prepared with ammoniated water; the dry ingre
lem of contamination of the second bath by the ?rst. ' As
dients comprised 35 to 40% of the total weight. These
aqueous coatings were then applied to a ?exible paper
‘base of the type previously described, driedin a conven
tional'drying oven and calendered to produce a smooth,
?at but not glossy surface. In some cases coatings
having as much as 65% dry ingredients were prepared
and successfully applied. Coatings were applied by con
ventional methodsand machinery. In nearly all cases
a further modi?cation I may combine the ?rst and sec-7
ond baths, ?ltering if necessary to remove any undesir
able precipitate; the resulting solution or the supernatant
liquid, in cases where ?ltrationis necessary, may then be
applied to the non-planographic coated base which,af_ter
drying and cutting to size, can be used with excellent"
success as a planographic printing plate on a conven~
coatings were applied simultaneously or singly to both 55 tional offset printing press. In applying ‘any. of the
sides of the paper base in order to reduce curl. In some
solutions described in the foregoing I prefer toobtain
cases the surface of the dried coating was bu?ed orother- '
-'Wi_se treated'to produce a dull or matte ?nish. Coated
papers prepared in the indicated manner were then ready,
without further preparation or treatment, for the appli
cation of the solution or solutions having the power to
impart planographic properties.
a For my planographic' solution or solutions I use a so
complete saturation of the coating and its supporting base
but I have found that it is also possible to make a sat
isfactory product even though complete saturation may
not ‘be achieved; thus I may apply my solutions by a
rapid passage-or dip ‘of the coated base or Imay apply
the solutions to only one side of the coated base as by
a. rotogravure roll, squeeze rolls, or similar means and,
lution containing less than 50% by volume of water and
preferably a solution containing less than ‘10% by vol 65 thus, impart planographic properties to only one side of
ume of‘water inorder- to avoid wrinkling, cockling, and
other di?iculties which seemingly always accompany the
the hitherto nonplanographic coated base. The only re
quirement of the method of application appears to be
application to paper of aqueous solutions or coatings.
that no excess of solution prior to, drying or solid
The non-aqueous solvents in this solution may include
ingredients after drying shall be left on the surface of
acetone, diethyliketone, methyl ethyl ketone, methyl iso 70 the coated ‘base thus treated; such excesses result in loose
butyl ketone, toluene, xylene, benzene, petroleum ether,
residues'which, unless removed, contribute to poor images
and to-toning or 'scumming of the non-image areas.
methyl alcohol, ethyl alcohol, isopropyl alcohol, glycerine,
ethylene glycol, polyethylene glycol, ethyl acetate, ethyl
Following are examples of essentially non-aqueous
proprionate, butylacetate, dibutyl ether and other similar
solutions used in practicingmy invention by the two-bath
liquids—-all have been used with more or less success.
or two-‘solution process as hereinbefore described.
3,083,639
5
6
Silicate-Containing Solutions
or two-solution process one ?nds that, since the second
bath sooner or later becomes contaminated by liquid resi
[Parts by volume]
Con~
densed
Ethyl
dues entering along with the still-undried coated paper
which has just passed through the ?rst bath, it is neces
95%
Ethanol
Methyl
Ethyl
Ketone
Water
Cone.
Acid
Silicate
Example l1___Example 12
Example 13
Example 14
Example 15.
129
170
90
60
100
100
100
100
100
100
200
200
200
200
200
30
40
21
21
25
2
2
2
2
2
Example 16 _________ -_
100
100
200
S0
2
sary to ?lter the second bath continuously in order to
remove extraneous matter. In practical operations the
necessary equipment may not be available. In conse
quence in the ?rst modi?cation of my process the second
bath is eliminated and instead the coated base, having no
10 surface excess but still bearing in liquid form a portion
of the first bath as given in Examples l1~2'2, is passed
brie?y through a chamber containing Volatile amines or
ammoniacal vapor after which the paper thus treated is
thoroughly dried. I have found that this vapor treatment
Examples 17-22: Identical with Examples ll~li6 except 15 is most efficacious and allows for highest running speeds
if the temperature in the chamber is maintained at least
as high as 100° F. but no higher than 200° F. Agita—
tion of the vapors of the chamber is very bene?cial and
that to each hundred parts by weight of solution is
added between 5 and 15 parts by weight of a humectant
chemical; glycerine, polyethylene glycol of molecular
allows rapid completion of the neutralization reactions,
weight 500 to 2090, and ethylene glycol are all satis
factory.
In Examples l1-22 concentrated hydrochloric acid is
used. Equally satisfactory results are obtained with
20 however care must be taken to avoid prolonged exposure
inasmuch as any softening of the coating or substantial
effect on the base-support itself would necessitate later
calendering and would thus defeat the essential purpose
of the process~which is its simplicity. It is a vital and
sulfuric acid or trichloroacetic acid.
In preparing the solutions of Examples l1-22 all in
gredients except the acid are mixed together, than the 25 important part of this invention that no obvious softening
or plasticization of the coating occurs in the rather ?eet
acid is added and the solution is agitated for twenty
ing exposure to solutions or vapors.
minutes after which it is ready to apply according to
As a further modi?cation and simpli?cation of the proc
the methods previously described.
ess I combine the ?rst bath with the second bath and treat
The solutions of Examples 11-22 are the “?rst” 0r
silicate-containing solutions. Examples of the “second” 30 a non-planographic coated base with this combined bath’
and thereby impart planographic properties equivalent
or alkaline solutions now follow.
in all essential respects to those obtained by the two
bath process or by the one-bath-plus-vapor-chamber proc
Alkaline Solutions
35
Alkaline
Alkaline Agent
Solvent Mixture
P‘g‘ggngy
Weight
Example 23..___ 132K011); ________ __ acetone-methanol 1:1__
Example 24" __ Ba(OH)2_ ...... -- methyl ethyl ketone-
11-22 with any of the alkaline solutions of Examples
2348 noting, however, that certain combinations some
2
2
times give better results, in terms of planographic plate per
methanol 111.
Example 25_.___
Example 26_____
2
1
Example 27_____
_ _-__-do _______________ _-
%
Example 28_-__-
methyl ethyl ketonemethanol 1% '1
2
Example 29-____ NHlOH (28%) ____ -_
2
Example 30_-__- NHOH (28%)_____
6
formance, than others depending on the porosity of the
coating, weight of coating, formulation, method of appli
cation, and so on.
ples 11-22 on bases bearing any one of the coatings of
Examples ll~l0 although in practical operations it will be
found that, depending on coating method, coating weight,
porosity, formulation and other factors the combination
Depending on the solvents and the
45 alkaline agent it may sometimes be necessary to ?lter the
alkaline solutions, which result when the silicate solution
is combined with the alkaline solution, in order to remove
Any one of the alkaline solutions of Examples 23—28
may be used to follow any one of the solutions of Exam
ess hereinbefore described. Furthermore -I ?nd that it is
possible to proceed thus with ?exible bases bearing any
of the non-planographic coatings of Examples 1-10 and
with any combination of the silicate solutions of Examples
50
objectionable residues which may otherwise be present
and which would produce inferior planographic proper
ties.
In order to eliminate the need for ?ltration and
in order to simplify further the preparation of this bath
it is possible to prepare the bath, without the use of an
acid, by merely adding the indicated amount of ammoni
um hydroxide or an equivalent amount of triethanol
of solutions which gives the best results may vary con 55
amine directly to the solvent solution containing the re
siderably from one coated base to the next.
quired amount of silicate ester; in such situations there
It is of signi?cance to note that if the acid is omitted
from the ?rst bath the application of the second bath Will
not result in the full development of planographic proper
ties whereas complete development of planographic prop
erties takes place in a matter of seconds when the ?rst
solution is prepared according to one of the Examples
1\l—22; this fact is taken as indicating that in the ?rst bath
is no need for the addition of extra water inasmuch as
sufficient is present in the 28% ammonium hydroxide;
furthermore, the acids used in the two-bath procedure may
also be omitted. Solutions prepared by the direct addi
tion of a solution of alkaline materials without the prior
addition of acids may require a somewhat longer period
for hydrolysis before being ready for use but are never
the hydrolysis is only partial and is completed in situ by
the application of the second bath. Furthermore, plano 65 theless entirely satisfactory for imparting planographic
properties to otherwise non-planographic coatings. While
graphic properties are only slightly developed or are not
bases such as sodium hydroxide and barium hydroxide
developed at all if, between baths, the coating and its
may be substituted for ammonium hydroxide or triethanol
surface are completely dried; this is true even though the
coating may again be treated with a water-containing but 70 amine or other liquid base the solution then requires ?l
non-silicate-containing solution prior to application of the
second bath. Thus it is clear the two-bath process does
not merely consist of applying ordinary inorganic silicates
dissolved or suspended in a largely organic solution.
tration prior to use in order to remove objectionable
residues.
As speci?c examples of plates which have been made by
my process and its modi?cations as hereinbefore de
In practicing my invention by the foregoing two-bath 75 scribed and to provide speci?c indication of the results
3,083,639
7
8
and performance which canube thus obtained I give the
following:
a
'
of the surface removed, to retain a newly-imparted image
while at the same time retaining the non-imaged areas
of the abraded portion in av cleanand hydrophilic con
dition. .It. is further noted that the non-planographic
r
' 'rwonx'rnrnoonnunn
Coating
' Second
asin
-
Example
N o.
7'
5
’
as in
perform satisfactorily but develop deep tone overall after
Example
No.
Example 31.--
..
Example 32
Example 33
Example 34..
Example35--.
_.
'
3
11
11.
5
1l_ _
5
11 plus 10 parts polyethylene
.
28
28
_
29
28
sodium silicate or ammonium silicate prepared by dissolv;
glycol '1000 per. 100 of solu~
tion.
Example 36._---_.
perhaps 25 revolutions. of the press and-no-amount- of
press adjustment can compensate for the absence of the
essential planographic qualities. It is further noted that:
efforts to produce essentially the same end-results through
the use of essentially non-aqueous solutions of- silicic acid
28
,4
5
5’
ing'or attempting to dissolve said compounds in various
solvents and solvent mixtures have proved, in all cases,
fruitless. It is further'noted that aqueous solutions or
-
11 ____________________________ _ ,
30
ONE-BATH PLUS VAPOR-CHAMBER PROCEDURE
Example 37 _____ __
5
-11 ___________________________ ._
none.
Example38 _____ __
5
11 plus 10 parts polyethylene
none.
coated papers used as bases in these examples do not,
when run as planographic platesgon a conventional press,
Bath
First Bath as in Example No.
glycol 1000 per 100 of solu
tion.
dispersions containing such compounds as silicic acid,
sodium silicate, ammonium silicate, silica or barium sili
cate invariably cause cocklingor wrinkling, of the sheet
20 andusually softening of the coating too, whereas these
disadvantages rarely, if ever, are found in the practice
of my invention according to the examples listed. ' It is
ONE-BATH PROCEDURE
further noted that the use of these aqueous dispersions or
Example 39 _____ ._
Example 40
'
Example 41.
Example 42_
__
Example 43 _____ __
3
solutions when applied to the coated sheet, for an ex
baths 11 and 28 combined; pH above 8.
4
Do;
6
5
Do.
baths 11 and 30 combined; pH above 8.
6
bath 11 lacking only acid; 10% NH4OH
25 posure period twice as long as commonly used in the ap
plication of my essentially non-aqueous solutions, fails to
impart planographic properties to any substantial depth
(28%) directly added; pH above 8.
of the coating. It is further noted that in order to-obtain.
planographic properties of any consequence through the
The ham used in preparing the plates of Examples 30 application of these aqueous solutions, dispersions, or
31-43 was a smooth, strong, calendered, water-resistant
paper such'as described earlier in this speci?cation; it
aquasols it is necessary to apply on a dry basis at least
2 to 3 pounds of silica or silicates per 3300 square feet
of surface whereas in the practice of my invention the
added weight is never more than 1.5 pounds per 3300
ing it rwas treated in accordance with the procedures 35 square feet ‘of surface and more commonly is less than
carried‘ approximately 15 pounds of non-planographic
coating per 3300 square feet of surface. After calender
previously described and in accordance with the speci?c
steps of Examples 3l.—43; the treatment impartedrscarcely
one-half pound of additional weight per 3300 square feet.
of. surface.
1.0 pound perv 3300square feet of surface.
In extending and broading still further the possible
application of my invention 11' have also applied the art
.
In making press runs with these plates on a conventional 40
oifset press using conventional inks and solutions the
following results were noted;
Plates from
Performance
Example N o.
‘200 excellent copies; then began to lose image.
300 excellent copies; then began to lose image.
1,500 excellent copies; no, loss of image.
LOGO-excellent copies; slight loss of image.
500 excellent copies; surface somewhat greasy.
1,000 excellent copies; slight loss of image.
1,000 excellent copies; no loss of image.
1,000 excellent copies; surtacesomewbat greasy.
200 clgpies; not su?iciently hydrophilic.
taught in Examples 11-43 to coated surfaces already’
having planographic properties. Thus, I have treated in
accordance with Examples 11,-43, paper planographic
plates such as are commercially available in the open
market and have found somefenhancement of plano
graphic properties. Thus it will be obvious to those
skilled in the art that the manufacture of existing plano
graphic plates can be simpli?ed and the product im
proved by utilizing my essential discovery in treating’
coated surfaces already possessed of ‘planographic prop;
50 erties.
What-I claim as new is:
, 1. The process'of making a planographic plate com-~
prising treating a ?exible paper base having a non-plano—
graphic coating with an acidi?ed solution of a lower
1,50%)excellent
copies; no loss of image.
0.
55 alkyl silicate ester in a solvent having less than 50%
by volume of water, and then-treating said coated base
‘From the» foregoing results it is clear that a soluble
with ‘an alkaline solution in an organic solvent, thereby
liquid base may yield superiorresults whenever the one
providing a planographic surface onsaid base.
'
bath process is used. Itappears clear that the barium
,2. The process of making a planographic plate com-‘
hydroxide, which is quite satisfactory for a two-bath sys 60 prising coating a ?exible base suii’iciently smooth for
tem, ‘precipitates too much of the silicate and therefore
planographic printing with a non-planographic layer,
the ability to impart planographic properties is impaired.
depositing a lower alkyl silicate ester on and in said layer
In the Examples 3143 it is noted that no calendering
from'an'essentially organic solution containing less than
or other treatment, following the application of the plane
graphic solutions, is necessary in order to obtain satis 65 50% by. volume of water, and exposing the deposited
o.
Do.
factory plates. Furthermore, it is noted that the plates
run well in every respect and exhibit a‘ strikingability
to develop-rapidly the printed image While at 'the‘same '
layer to alkaline vapors, thereby providinga planographic
coating on saidbase.
3. The process of making a planographic plate com-g
prising coating a ?exible paper base with a non-Plano
time maintainingnon-imaged areas free from scumming
and background “tone due to adherent ink. Furthermore, 70 graphic layer comprised essentially of a mineral pigment.
and adhesivessclected from the class consisting of pro
it‘ is notedthatplanographic printing qualities areim
tein and resinous adhesives, depositing particles of par.
parted not'only-to thelsurface but also in depth-and-are
tially hydrolyzed ethyl silicate onand in saidlayer from.
an essentially organic solution containingless than 50%
withstand abrasive wear and,‘ after thus having a portion 75 by volume of water, and exposing. the-deposited layer to.
in no sense a mere surface treatment; the presence of
treatment in depth isrevidenced by these plates’ ability ‘to
8,083,639
10
8. The process de?ned by claim 7 wherein the solution
and alkaline agent are ?rst combined and then applied
alkaline vapors to complete the hydrolysis of the ethyl
silicate.
4. The process of making a planographic plate which
to the base.
9. The process of making a planographic plate which
comprises applying to a coated ?exible paper base a com
position formed by dissolving a lower alkyl silicate in an
essentially organic solvent containing Water in an amount
less than 50 percent by volume and adding thereto an
alkaline agent in an amount e?ective to hydrolyze said
silicate, and drying said base thereby providing a plane
graphic coating thereon.
comprises applying to a coated ?exible paper base a solu
tion of ethyl silicate in an essentially organic solvent con
taining less than 50 percent by volume of water and an
alkaline agent e?’ective to hydrolyze said silicate, and
drying said base, thereby providing a planographic c'oat
10 ing thereon.
5. The process de?ned by claim 4 wherein the paper
base is coated with a composition comprising mineral
pigment and adhesive.
6. The process of making a planographic plate which
10. The process of making a planographic plate which
comprises applying to a coated ?exible paper base an
acidi?ed solution of a lower alkyl silicate in an essen
tially organic solvent containing less than 50 percent by
comprises applying to a ?exible paper base having a coat 15 volume of water and an alkaline agent e?ective to hydro
lyze said silicate, and drying said base, thereby providing
ing comprising mineral pigment and adhesive, a com
a planographic coating thereon.
position formed by dissolving ethyl silicate in an essen~
tially organic solvent containing water in an amount less
References Cited in the ?le of this patent
than 50 percent by volume and adding thereto an alkaline
20
UNITED STATES PATENTS
agent in an amount e?ective to hydrolyze said silicate, and
drying said base thereby providing a planographic coat
1,809,755
King et al ______________ .... vJune 9, 1931
ing thereon.
7. The process of making a planographic plate which
comprises applying to a coated ?exible paper base a solu 25
tion of a ‘lower alkyl silicate in an essentially organic
solvent containing less than 50 percent by volume of
Water and an alkaline agent e?ective to hydrolyze said
silicate, and drying said base, thereby providing a plane
graphic coating thereon.
30
2,027,931
2,053,4742,132,443
2,156,100
2,329,632
2,534,650
2,681,617
2,692,826
Ray __________________ __ Jan. 4,
Graves et a1 ___________ __ Sept. 8,
Simons ______________ __. Oct. 11,
Simons ______________ __ Apr. 25,
Marsden _____________ __ Sept. 14,
Worthen _____________ __ Dec. 19,
Worthen et a1 _________ .._. June 22,
Neugebauer et a1 _______ __ Oct. 26,
1936
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